Clathrate compound, method for controlling concentration of aqueous agricultural chemical active ingredient solution, and agricultural chemical formulation

ABSTRACT

A clathrate compound containing a polymolecular host compound as a host compound and an agricultural chemical active ingredient having a saturated solubility in water at 25° C. of not less than 500 ppm as a guest compound.

CROSS-REFERENCE TO PRIOR APPLICATION

This is a divisional of application Ser. No. 11/571,975 filed Jan. 11,2007, which is a National Stage Application of PCT/JP2005/012837 filedJul. 12, 2005, and claims the benefit of Japanese Patent ApplicationNos. 2004-205905 filed Jul. 13, 2004 and 2004-264479 filed Sep. 10,2004. The entire disclosure of the prior applications are herebyincorporated by reference herein in its entirety.

TECHNICAL FIELD

The present invention relates to a clathrate compound containing apolymolecular host compound as a host compound and an agriculturalchemical active ingredient having ready water-solubility as a guestcompound, a method for controlling the concentration of an aqueousagricultural chemical active ingredient solution, and an agriculturalchemical formulation containing the clathrate compound.

BACKGROUND ART

An agricultural chemical active ingredient has generally been used as anagricultural chemical formulation after being formulated. Examples ofthe agricultural chemical formulation include powders, granules,wettable powders, wettable granules, water-soluble agents, water-solubleliquid formulations, emulsifiable concentrates, and sol formulations.

The agricultural chemical active ingredient having readywater-solubility, for example, acetamiprid, is usually used forwater-soluble chemicals, granules, and wettable powders.

Recently, formulations as well as application methods thereof have beendeveloped so as to enhance the safety to humans and environments and topromote laborsaving. For example, formulations have been required whichcan be stably stored for a long period and do not lose theiragricultural chemical potency for a long period even in soil, and whichcan also exhibit agricultural chemical potency for a long period bycontrolled release of the agricultural chemical active ingredients.

In contrast, in connection with the present invention, some clathratecompounds containing a tetrakisphenolethane compound as a host compoundand a pharmacologic agent as a guest compound are known. For example,Patent Literature 1 describes an epoxy adhesive in which a guestcompound such as a curing agent for epoxy resin is included by apolymolecular host compound, and Patent Literature 2 describes ableaching powder-free slime control agent in which an antibacterialagent such as 5-chloro-2-methyl-4-isothiazolin-3-one is included by apolymolecular host compound such as tetrakisphenols.

-   [Patent Literature 1] Japanese Unexamined Patent Application, First    Publication No. Hei 5-194711-   [Patent Literature 2] Japanese Unexamined Patent Application, First    Publication No. 2000-327509

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a clathrate compoundcontaining a polymolecular host compound as a host compound and anagricultural chemical active ingredient having ready water-solubility asa guest compound, a method for controlling the concentration of anaqueous agricultural chemical active ingredient solution, and anagricultural chemical formulation which is excellent in sustainedreleasability, storage stability and stability in soil.

Means for Solving the Problems

The present inventors have prepared and evaluated a clathrate compoundcontaining a polymolecular host compound as a host compound and anagricultural chemical active ingredient having ready water-solubility,for example, acetamiprid, as a guest compound, and succeeded in thepreparation of the objective clathrate compound. They have found thatthe use of the resulting clathrate compound makes it possible tomaintain saturated solubility of the agricultural chemical activeingredient in water within a predetermined concentration range, and toobtain sol-like agricultural chemical formulation (sol formulation)which is excellent in sustained releasability, storage stability andstability in soil. Thus, the present invention has been completed.

According to a first aspect of the present invention, a clathratecompound characterized by containing a polymolecular host compound as ahost compound, and an agricultural chemical active ingredient havingsaturated solubility in water at 25° C. of not less than 500 ppm as aguest compound are provided.

In the clathrate compound of the present invention, the polymolecularhost compound is preferably a compound having two or more hydroxylgroups and two or more aromatic groups in the molecule thereof and ismore preferably either of a tetrakisphenol compound represented byformula (I):

(wherein X represents (CH₂)_(n) (n represents an integer of 0 to 3) or aphenylene group which may have a substituent, and R¹ to R⁸ eachindependently represents a hydrogen atom, an alkyl group having 1 to 6carbon atoms, a phenyl group which may have a substituent, a halogenatom or an alkoxyl group having 1 to 6 carbon atoms), or ahydroxybenzophenone compound represented by formula (II):

(wherein R⁹ and R¹⁰ each independently represents an alkyl group having1 to 6 carbon atoms, a halogen atom or an alkoxyl group having 1 to 6carbon atoms, r and s each independently represents an integer of 0 to4, and p and q each independently represents an integer of 1 to 4).

In the clathrate compound of the present invention, the agriculturalchemical active ingredient is preferably a neonicotinoid compound andthe neonicotinoid compound is more preferably at least one selected fromthe group consisting of nitenpyram, imidacloprid, acetamiprid,thiamethoxam, clotianidin, thiacloprid and dinotefuran.

According to a second aspect of the present invention, a method forcontrolling the concentration of an aqueous agricultural chemical activeingredient solution is provided, characterized by containing a step ofmaintaining a saturated solubility of the agricultural chemical activeingredient in water within a predetermined concentration range byincluding the agricultural chemical active ingredient having saturatedsolubility in water at 25° C. of not less than 500 ppm in an interiorspace formed of a polymolecular host compound.

In the concentration control method of the present invention, it ispreferable that the saturated solubility of the agricultural chemicalactive ingredient in water be maintained within a predeterminedconcentration range by suitably selecting the polymolecular hostcompound and including the agricultural chemical active ingredient in aninterior space formed of the polymolecular host compound.

In the concentration control method of the present invention, thepolymolecular host compound is preferably a compound having two or morehydroxyl groups and two or more aromatic groups in the molecule thereof,and more preferably is either of the tetrakisphenol compound representedby formula (I) or the hydroxybenzophenone compound represented byformula (II).

In the concentration control method of the present invention, theagricultural chemical active ingredient is preferably a neonicotinoidcompound and the neonicotinoid compound is more preferably at least oneselected from the group consisting of nitenpyram, imidacloprid,acetamiprid, thiamethoxam, clotianidin, thiacloprid and dinotefuran.

According to a third aspect of the present invention, an agriculturalchemical formulation is provided, characterized by containing theclathrate compound of the present invention.

The agricultural chemical formulation of the present invention ispreferably a seed treatment agent.

The agricultural chemical formulation of the present invention ispreferably a sol formulation.

According to a fourth aspect of the present invention, an agriculturalactive composition is provided, characterized by containing theclathrate compound of the present invention and a synthetic pyrethroid.

An agricultural chemical formulation is also provided, characterized bycontaining the agricultural active composition of the present invention.The agricultural chemical formulation is preferably a seed treatmentagent and the agricultural chemical formulation is preferably a solformulation.

Effects of the Invention

According to the clathrate compound of the present invention, anagricultural chemical formulation can be prepared which can maintainsaturated solubility of an agricultural chemical active ingredienthaving ready water-solubility within a predetermined concentration rangeand is also excellent in sustained releasability, storage stability andstability in soil.

According to the concentration control method of the present invention,it is made possible to maintain saturated solubility of an agriculturalchemical active ingredient having ready water-solubility within apredetermined concentration range. Consequently, elution of theagricultural chemical active ingredient into moisture in the soil can becontrolled and thus the persistence of potency thereof is not lowered byenvironmental change such as rainfall or the like.

The agricultural chemical formulation of the present invention isexcellent in sustained releasability, storage stability and stability insoil and can efficiently exhibit active efficacy, and is alsoenvironmentally friendly.

The agricultural active composition of the present invention can exhibitactive efficacy more efficiently.

In the agricultural chemical formulation containing the clathratecompound of the present invention as a sol formulation, neither particlegrowth nor caking may substantially occur.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing a ¹H-NMR spectrum of Clathrate compound 1.

FIG. 2 is a graph showing the measurement results of XRD of Clathratecompound 1.

FIG. 3 is a graph showing the measurement results of TG-DTA of Clathratecompound 1.

FIG. 4 is a graph showing a ¹H-NMR spectrum of Clathrate compound 2.

FIG. 5 is a graph showing the measurement results of XRD of Clathratecompound 2.

FIG. 6 is a graph showing the measurement results of TG-DTA of Clathratecompound 2.

FIG. 7 is a graph showing a ¹H-NMR spectrum of Clathrate compound 3.

FIG. 8 is a graph showing the measurement results of XRD of Clathratecompound 3.

FIG. 9 is a graph showing the measurement results of TG-DTA of Clathratecompound 3.

FIG. 10 is a graph showing a ¹H-NMR spectrum of Clathrate compound 4.

FIG. 11 is a graph showing an IR spectrum of Clathrate compound 4.

FIG. 12 is a graph showing the measurement results of XRD of Clathratecompound 4.

FIG. 13 is a graph showing the measurement results of TG-DTA ofClathrate compound 4.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will now be described in detail with respect tothe following items: 1) a clathrate compound, 2) a method forcontrolling the concentration of an aqueous agricultural chemical activeingredient solution, 3) an agricultural chemical formulation, and 4) anagricultural active composition.

1) Clathrate Compound

The clathrate compound of the present invention is characterized bycontaining a polymolecular host compound as a host compound and anagricultural chemical active ingredient having saturated solubility inwater at 25° C. of not less than 500 ppm as a guest compound.

The polymolecular host compound used in the present invention is acompound in which plural molecules are combined via a hydrogen bond toform a crystal with an interior space and in which a guest compound canbe included in the space.

The polymolecular host compound used in the present invention is notspecifically limited as long as it is a compound having such a property.

Examples of the polymolecular host compound include compounds having onearomatic group and one hydroxyl group in a molecule thereof, such asphenol, o-chlorophenol, 2,4,6-trichlorophenol, p-chlorophenol,o-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, 2,6-dinitrophenol,2,4,6-trinitrophenol, p-t-butylphenol, and p-t-octylphenol;

compounds having one aromatic group and two hydroxyl groups in amolecule thereof, such as t-butylhydroquinone and2,5-di-t-butylhydroquinone;

compounds having two or more aromatic groups and two or more hydroxylgroups in a molecule thereof, such asα,α,α′,α′-tetraphenyl-1,1′-biphenyl-2,2′-dimethanol,4,4′-cyclohexilidenebisphenol, 4,4′-methylenebisphenol,4,4′-ethylidenebisphenol, 5,5′-methylenedisalicylic acid,bis(4-hydroxyphenyl)sulfide,4,4′-butylidenebis(3-methyl-6-t-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol),4,4′-(1-phenylethylidene)bisphenol,2,5-bis(2,4-dimethylphenyl)hydroquinone,1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol,1,1,4,4-tetraphenyl-2-butyne-1,4-diol,1,1,2,2-tetraphenylethane-1,2-diol,1,1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyne-1,6-diol,9,9′-bianthracene,9,10-bis(4-methylphenyl)-9,10-dihydroanthracene-9,10-diol,9,10-diphenyl-9,10-dihydroanthracene-9,10-diol, 1,1-bis-2-naphthol, thetetrakisphenol compounds represented by formula (I), and thehydroxybenzophenone compounds represented by formula (II); and

other polymolecular host compounds such as1,4-diazabicyclo-[2.2.2]-octane, granular cornstarch (Porous Y-20),5,5-dimethylhydantoin, N-phenylmaleimide, and 9,9′-bianthracene.

These polymolecular host compounds can be used alone or in combinationof at least two kinds thereof.

Among these, a compound having two or more aromatic groups and two ormore hydroxyl groups in a molecule thereof is preferable and atetrakisphenol compound represented by formula (I) or ahydroxybenzophenone compound represented by formula (II) is morepreferable because a clathrate compound containing an agriculturalchemical active ingredient having saturated solubility in water at 25°C. of not less than 500 ppm as a guest compound can be obtainedefficiently and also an agricultural chemical formulation havingexcellent sustained releasability, storage stability and stability insoil can be obtained.

In formula (I), X represents (CH₂)_(n), or a phenylene group which mayhave a substituent.

n represents an integer of 0 to 3 and is preferably 0.

The phenylene group may be a p-phenylene group, an m-phenylene group oran o-phenylene group, but is preferably a p-phenylene group.

Examples of the substituent of the phenylene group which may have asubstituent include halogen atoms such as fluorine, chlorine, andbromine; alkyl groups such as a methyl group, ethyl group, and n-propylgroup; and alkoxy groups such as a methoxy group, ethoxy group, andn-propoxy group. Among these, a phenylene group having no substituent ispreferable.

R¹ to R⁸ each independently represents a hydrogen atom; an alkyl grouphaving 1 to 6 carbon atoms such as a methyl group, ethyl group, n-propylgroup, or isopropyl group; a phenyl group which may have a substituent,such as a phenyl group, 2-chlorophenyl group, 4-methylphenyl group,2,4-difluorophenyl group, 3,5-dimethoxyphenyl group, or2,4,6-trimethylphenyl group; a halogen atom such as fluorine, chlorine,or bromine; or an alkoxyl group having 1 to 6 carbon atoms, such as amethoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxygroup, or t-butoxy group.

Specific examples of the compound represented by formula (I) include1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP),1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-chloro-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-dichloro-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-bromo-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-dibromo-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-t-butyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-fluoro-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-difluoro-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-methoxy-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-chloro-5-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-bromo-5-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-methoxy-5-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-t-butyl-5-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-chloro-5-bromo-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis(3-chloro-5-phenyl-4-hydroxyphenyl)ethane,1,1,2,2-tetrakis[(4-hydroxy-3-phenyl)phenyl]ethane,

-   1,1,3,3-tetrakis(4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-methyl-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-dimethyl-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-chloro-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-dichloro-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-bromo-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-dibromo-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-phenyl-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-diphenyl-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-methoxy-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3-t-butyl-4-hydroxyphenyl)propane,    1,1,3,3-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)propane,-   1,1,4,4-tetrakis(4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3-methyl-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3,5-dimethyl-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3-chloro-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3,5-dichloro-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3-methoxy-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3-bromo-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3,5-dibromo-4-hydroxyphenyl)butane,    1,1,4,4-tetrakis(3-t-butyl-4-hydroxyphenyl)butane, and    1,1,4,4-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)butane.

Specific examples thereof further includeα,α,α′,α′-tetrakis(4-hydroxyphenyl)-p-xylene,α,α,α′,α′-tetrakis(4-hydroxyphenyl)-m-xylene,α,α,α′,α′-tetrakis(4-hydroxyphenyl)-o-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-methylphenyl)-p-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-chlorophenyl)-p-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-ethylphenyl)-p-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-isopropylphenyl)-p-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-chlorophenyl)-m-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-methylphenyl)-m-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-ethylphenyl)-m-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-methylphenyl)-o-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-chlorophenyl)-o-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-ethylphenyl)-o-xylene,α,α,α′,α′-tetrakis(4-hydroxy-3-isopropylphenyl)-o-xylene,

-   α,α,α′,α′-tetrakis(4-hydroxy-3-t-butylphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-bromophenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-iodophenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-methoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-ethoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-isopropoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-t-butoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxy-4-chlorophenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxy-4-bromophenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxy-4-iodophenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxy-4-methoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(3-hydroxy-4-ethoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(2-hydroxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(2-hydroxy-4-chlorophenyl)-p-xylene,    α,α,α′,α′-tetrakis(2-hydroxy-4-methylphenyl)-p-xylene,    α,α,α′,α′-tetrakis(2-hydroxy-4-methoxyphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3,5-dichlorophenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3,5-dimethylphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxy-3-chloro-5-methylphenyl)-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxyphenyl)-3-chloro-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxyphenyl)-3-methyl-p-xylene,    α,α,α′,α′-tetrakis(4-hydroxyphenyl)-3-methoxy-p-xylene,    α,α-bis(4-hydroxyphenyl)-α′,α′-bis(3-chloro-4-hydroxyphenyl)-p-xylene,    α,α-bis(4-hydroxyphenyl)-α′,α-bis(3-methyl-4-hydroxyphenyl)-p-xylene,    α,α-bis(4-hydroxyphenyl)-α′,α-bis(3-methoxy-4-hydroxyphenyl)-p-xylene,    α,α,α′-tris(4-hydroxyphenyl)-α′-3-chlorophenyl-p-xylene,    α,α,α′-tris(4-hydroxyphenyl)-α′-3-methylphenyl-p-xylene, and    α,α,α′-tris(4-hydroxyphenyl)-α′-3-methoxyphenyl-p-xylene.

In formula (II), R⁹ and R¹⁰ each independently represents an alkyl grouphaving 1 to 6 carbon atoms, a halogen atom or an alkoxyl group having 1to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms, thehalogen atom and the alkoxyl group having 1 to 6 carbon atoms are thesame as those described as the alkyl group having 1 to 6 carbon atoms,the halogen atom and the alkoxyl group having 1 to 6 carbon atoms informula (I).

r and s each independently represents an integer of 0 to 4 and ispreferably 0. p and q each independently represents an integer of 1 to 4and is preferably 1 or 2.

Specific examples of the compound represented by formula (II) include4,4′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone,3,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone,2,3′-dihydroxybenzophenone, 2,2′-dihydroxybenzophenone,4,4′-dihydroxy-2-methylbenzophenone,4,4′-dihydroxy-3-methylbenzophenone,4,4′-dihydroxy-2-chlorobenzophenone,4,4′-dihydroxy-3-chlorobenzophenone,4,4′-dihydroxy-2-methoxybenzophenone,4,4′-dihydroxy-2-methoxybenzophenone,4,4′-dihydroxy-2,2′-dimethylbenzophenone,4,4′-dihydroxy-3,3′-dimethylbenzophenone,4,4′-dihydroxy-2,2′-dichlorobenzophenone,4,4′-dihydroxy-3,3′-dichlorobenzophenone,4,4′-dihydroxy-2,2′-dimethoxybenzophenone,4,4′-dihydroxy-2,2′-dimethoxybenzophenone,3,3′-dihydroxy-2,2′-dimethylbenzophenone,3,3′-dihydroxy-4,4′-dimethylbenzophenone,2,2′-dihydroxy-3,3′-dimethylbenzophenone,2,2′-dihydroxy-4,4′-dimethylbenzophenone,

-   2,2′,4,4′-tetrahydroxybenzophenone,    2,2′,3,3′-tetrahydroxybenzophenone,    3,3′,4,4′-tetrahydroxybenzophenone,    2,2′,3,4′-tetrahydroxybenzophenone,    3,3′,2,4′-tetrahydroxybenzophenone,    4,4′,3,2′-tetrahydroxybenzophenone,    2,3,4,4′-tetrahydroxybenzophenone,    2,2′,4,4′-tetrahydroxy-3,3′-dimethylbenzophenone,    2,2′,4,4′-tetrahydroxy-3,3′-dichlorobenzophenone, and    2,2′,4,4′-tetrahydroxy-3,3′-dimethoxybenzophenone.

The agricultural chemical active ingredient to be used is notspecifically limited as long as it is an agricultural chemical activeingredient having saturated solubility in water at 25° C. of not lessthan 500 ppm (also referred to as an “agricultural chemical activeingredient having ready water-solubility”, hereinafter).

Examples of the agricultural chemical active ingredient having readywater-solubility include neonicotinoid compounds such as(E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovinylidenediamine[common name: nitenpyram, aqueous solubility: about 2000 ppm],(E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine[common name: acetamiprid, aqueous solubility in water: 4200 ppm (25°C.)], 1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine[common name: imidacloprid, aqueous solubility: 510 ppm (20° C.)],3-(2-chloro-1,3-thiazole-5-methyl-1,3,5-oxadiazinan-4-ylidene [commonname: thiamethoxam, aqueous solubility: 4100 ppm (25° C.)],(E)-1-(2-chloro-1,3-thiazol-5-ylmethyl-3-methyl-2-nitroguanidine [commonname: clotianidin, aqueous solubility: 0.327 g/L (20° C.)],3-(6-chloro-3-pyridylmethyl)-1,3-thiazolidin-2-ylidenecyanamide (commonname: thiacloprid), and(RS)-1-methyl-2-nitro-3-(tetrahydro-3-furylmethyl)guanidine (commonname: dinotefuran);

phosphorus compounds such as O,S-dimethyl-N-acetylphosphoroamide thioate[common name: acephate, about 650000 ppm],N2-(4-chloro-o-toluyl)-N1,N1-dimethylformamide [aqueous solubility: 250ppm (20° C.)], and 2,2-dichlorovinyldimethyl phosphate [common name:DDVP, aqueous solubility: about 1000 ppm (room temperature)]; carbamatecompounds such as2,2-dimethyl-1,3-benzodioxol-4-yl-methylcarbamate•hydrochloride [commonname: bendiocarb, aqueous solubility: 26000 ppm (25° C.)],S,S′-2-dimethylaminotrimethylene-bis(thiocarbamate) [common name:cartap, aqueous solubility: 200000 ppm (25° C.)], and2-ethylthiomethylphenylmethylcarbamate [common name:ethiofencarb,aqueous solubility: 1800 ppm (20° C.)]; and

other insecticidal compounds such asS-methyl-N,N-dimethyl-N-methylcarbamoyloxy-1-thiooxam imidate [commonname: oxamyl, aqueous solubility: 280000 ppm],S-methyl-N-(methylcarbamoyloxy)thioacetoimidate [common name: methomyl,aqueous solubility: 58000 ppm], and 1,3-dichloropropene [common name:D-D, aqueous solubility: 2000 ppm].

Among these compounds, the agricultural chemical active ingredient ispreferably a neonicotinoid compound and the neonicotinoid compound ismore preferably at least one selected from the group consisting ofnitenpyram, imidacloprid, acetamiprid, thiamethoxam, clothianidin,thiacloprid and dinotefuran in the present invention.

These agricultural chemical active ingredients can be used alone or incombination of at least two kinds thereof mixed in an arbitrary ratio.Among these, acetamiprid is particularly preferable because it has highagricultural chemical activity and exerts remarkable effects in forminga clathrate compound.

The method for preparing the clathrate compound of the present inventionis not specifically limited and a conventionally known method forpreparing a clathrate compound using a polymolecular host compound canbe employed.

Specific examples of the method include (i) a method of adding apolymolecular host compound to a liquid agricultural chemical activeingredient, followed by stirring, (ii) a method of adding apolymolecular host compound to a solvent solution of a solidagricultural chemical active ingredient, followed by stirring, and (iii)a method of mixing a solid agricultural chemical active ingredient witha powdered polymolecular host compound.

When methods (i) to (iii) are employed, the stirring temperature isusually from room temperature to 100° C., and the stirring time isusually from several minutes to several tens of hours.

The mixing ratio of the polymolecular host compound to the agriculturalchemical active ingredient as the guest compound varies depending on thekind of compound to be used, and a ratio of the polymolecular hostcompound: the agricultural chemical active ingredient is generally from99:1 to 1:99 (parts by weight), a ratio of the polymolecular hostcompound: the agricultural chemical active ingredient is preferably from80:20 to 20:80 (parts by weight), a ratio of the polymolecular hostcompound: the agricultural chemical active ingredient is more preferablyfrom 60:40 to 35:65 (parts by weight).

Examples of the solvent to be used include water; alcohols such asmethanol and ethanol; esters such as ethyl acetate; and halogenatedhydrocarbons such as dichloromethane.

The amount of solvent is not specifically limited as long as it enablesstirring and mixing with ease as well as after-treatment with ease.

The objective clathrate compound can be isolated according toconventional separation and purification methods from the mixtureobtained by stirring.

The structure of the resulting clathrate compound can be checked bywell-known analytical methods such as NMR spectrometry, IR spectrometry,and mass spectrometry.

The obtained clathrate compound can be formed into a sol solution havinghigh dispersion stability, as described hereinafter.

The melting point of the obtained clathrate compound is not influencedby the agricultural chemical active ingredient or solvent to be used,but is influenced by the polymolecular host compound to be used. Forexample, when acetamiprid having a melting point of 96.25° C. is used asthe agricultural chemical active ingredient, a clathrate compound havinga melting point of about 165° C. is obtained by using1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP) as the polymolecular hostcompound, and a clathrate compound having a melting point of about 135°C. is obtained by using 2,2′,4,4′-tetrahydroxybenzophenone.

The clathrate compound of the present invention can be mixed with otherfungicides or insecticides so as to broaden the biological applicationrange. Specific examples to be mixed include, but are not limited to,the following.

Fungicides:

-   Copper agents; basic copper chloride, basic copper sulfate, and the    like.-   Sulfur agents; thiuram, zineb, maneb, mancozeb, ziram, propineb,    polycarbamate, and the like.-   Polyhaloalkylthio agent; captan, folpet, dichlorofluanide, and the    like.-   Organic chlorine agents; chlorothalonil, fthalide, and the like.-   Organophosphorus agents; IBP, EDDP, tolclofos-methyl, pyrazophos,    fosetyl, and the like.-   Benzimidazole agents; thiophanate-methyl, benomyl, carbendazim,    thiabendazole, and the like.-   Dicarboxyimide agents; iprodione, procymidone, vinclozolin,    fluoroimide, and the like.-   Carboxyamide agents; oxycarboxin, mepronil, flutolanil, tecloftalam,    trichlamide, pencycuron, and the like.-   Acylalanine agents; metalaxyl, oxadixyl, furalaxyl, and the like.-   Methoxyacrylate agents; kresoxim-methyl, azoxystrobin,    metominostrobin, and the like.-   Anilinopyrimidine agents; andpurine, mepanipyrim, pyrimethanil,    cyprodinil, and the like.-   SBI agents; triadimefon, triadimenol, bitertanol, myclobutanil,    hexaconazole, propiconazole, triflumizole, prochloraz, pefurazoate,    fenarimol, pyrifenox, triforine, flusilazole, etaconazole,    diclobutrazol, fluotrimazole, flutriafen, penconazole, diniconazole,    imazalil, tridemorph, fenpropimorph, buthiobate, epoxiconazole,    metoconazole, and the like.-   Antibiotics; polyoxin, blasticiden S, kasugamycin, validamycin,    dihydrostreptomycin sulfate, and the like. Others; propamocarb    hydrochloride, quintozene, hydroxyisoxazole, methasulfocarb,    anirazine, isoprothiolane, probenazole, chiomethionat, dithianon,    dinocap, diclomezine, ferimzone, fluazinam, pyroquilon,    tricyclazole, oxolinic acid, dithianon, iminoctadine acetate,    cymoxanil, pyrrolnitrin, methasulfocarb, diethofencarb, binapacryl,    lecithin, sodium bicarbonate, fenaminosulf, dodine, dimethomorph,    phenazine oxide, carpropamid, flusulfamide, fludioxonil, famoxadone,    and the like.

Insecticides/Acarcides:

-   Organophosphorus and carbamate insecticides; fenthion, fenitrothion,    diazinon, chlorpyrifos, ESP, vamidothion, phenthoate, dimethoate,    formothion, malathion, trichlorfon, thiometon, phosmet, dichlorvos,    acephate, EPBP, methyl parathion, oxydimeton-methyl, ethion,    salithion, cyanophos, isoxathion, pyridaphenthion, phosalone,    methidathion, sulprofos, chlorfenvinphos, tetrachlorvinphos,    dimethylvinphos, propaphos, isophenphos, ethylthiometon, profenofos,    pyraclofos, monocrotophos, azinphos-methyl, aldicarb, methomyl,    thiodicarb, carbofuran, carbosulfan, benfuracarb, furathiocarb,    propoxur, BPMC, MTMC, MIPC, carbaryl, pirimicarb, ethiofencarb,    phenoxycarb, and the like. Pyrethroid insecticides; permethrin,    cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pytethrin,    allethrin, tetramethrin, resmethrin, dimethrin, propathrin,    phenothrin, protryne, fluvalinate, cyfluthrin, cyhalothrin,    fucythrinate, ethofenprox, cycloprotryne, tralomethrin, silafluofen,    brofenprox, acrinathrin, and the like. Benzoylurea and other    insecticides; diflubenzuron, chlorfluazuron, hexaflumuron,    triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin,    pyriproxyfen, methoprene, benzoepin, diafenthiuron, acetamiprid,    imidacloprid, nitenpyram, fipronil, cartap, thiocyclam, bensultap,    nicotine sulphate, rotenone, metaldehyde, machine oil, microorganism    pesticides such as BT and insect pathogenic virues; pheromone    agents, and the like.

Nematicides; fenamiphos and fosthiazate

Acaricides; chlorobenzilate, phenisobromolate, dicofol, amitraz, BPPS,benzomate, hexathiazox, fenbutatin oxide, polynactin, chinomethionat,CPCBS, tetradifon, avermectin, milbemectin, clofentezine, cyhexatin,pyridaben, fenpyroxymate, tebufenpyrad, pyrimidifen, fenothiocarb,dienochlor, and the like.

Plant growth regulators: gibberellins (for example, gibberellin A3,gibberellin A4, gibberellin A7), IAA, NAA, and the like.

Herbicides:

-   Anilide herbicides; diflufenican, propanil, and the like.-   Chloroacetianilide herbicides; alachlor, pretilachlor, and the like.-   Aryloxyalkanoic acid herbicides; 2,4-D, 2,4-DB, and the like.-   Aryloxyphenoxyalkanoic acid herbicides; diclofop-methyl,    fenoxaprop-ethyl, and the like.-   Arylcarboxylic acid herbicides; dicamba, pyrithiobac, and the like.-   Imidazoline herbicides; imazaquin, imazethapyr, and the like.-   Urea herbicides; diuron, isoproturon, and the like.-   Carbamate herbicides; chlorpropham, phenmedipham, and the like.-   Thiocarbamate herbicides; thiobencarb, EPTC, and the like.-   Dinitroaniline herbicides; trifluralin, pendimethalin, and the like.-   Diphenyl ether herbicides; acifluorfen, fomesafen, and the like.-   Sulfonylurea herbicides; bensulfuron-methyl, nicosulfuron, and the    like.-   Triazinone herbicides; metribuzin, metamitron, and the like.-   Triazine herbicides; atrazine, cyanazin, and the like.-   Triazopyrimidine herbicides; flumetsulam, and the like.-   Nitrile herbicides; bromoxinil, dichlobenil, and the like.-   Phosphoric acid herbicides; glyphosate, glufosinate, and the like.-   Quaternary ammonium salt herbicides; paraquat, difenzoquat, and the    like.-   Cyclic imide herbicides; flumiclorac-pentyl, fluthiacet-methyl, and    the like.-   Benzoylaminopropionic acid herbicides; benzoylprop-ethyl,    furanprop-ethyl, and the like.-   Other herbicides; isoxaben, ethofumesate, oxadiazon, piperophos,    daimuron, bentazone, benfuresate, difenzoquat, naproanilide,    triazophenamide, quinchlorac, clomazone, sulcotrione, cinmethylin,    dithiopyr, pyrazolate, pyridate, and flupoxam, and cyclohexanedione    herbicides such as sethoxydim, tralkoxydim, and the like.

Synergists/Antidotes; octachlorodipropyl ether, piperonyl butoxide,cyneprin, IBTA, benoxacor, cloquintocet-methyl, ciometranil, dichlormid,fenchlorazole-ethyl, fencloram, flurazole, flaxofenimi, furilazole,mefenpyr-diethyl, MG191, naphthalic anhydride, oxabetrinil,neonicotinoid-based compounds, and the like.

Antibacterial/antifungal/antialgae agents; trialkyltriamine, ethanol,isopropyl alcohol, propyl alcohol, trisnitro, chlorobutanol, pronopol,glutaraldehyde, formaldehyde, α-bromcinnamaldehyde, scane M-8, caissonCG, NS-500W, BIT, n-butyl BIT, allyl isothiocyanate, thiobendazole,methyl 2-benzimidazolyl carbamate, lauricidine, biovan, triclocarban,halocarban, glasisicar, benzoic acid, sorbic acid, caprylic acid,propionic acid, 10-undecylenic acid, potassium sorbate, potassiumpropionate, potassium benzoate, monomagnesium phthalate, zincundecylenate, 8-hydroxyquinoline, copper quinoline, TMTD, triclosan,dichlohelanilide, tolyfluanid, milt protein, egg white lysozyme,benthiazole, sodium carbam, triazine, tebuconazole, hinokithiol,tetrachloroisophthalonitrile, tectamer 38, chlorhexidine gluconate,chlorhexidine hydrochloride, polyhexamethylene biguanide, polybiguanidehydrochloride, danthoprom, clidant, sodium pyrithion, zinc pyrithion,densil, kappa-pyrithion, thymol, isopropyl methyl phenol, OPP, phenol,butyl paraben, ethyl paraben, methyl parabenzen, propyl parabenzene,metacresol, orthocresol, paracresol, sodium orthophenyl phenol,chlorofen, parachlorophenol, parachloro methaxylate, parachlorocresol,fluorfolpet, polylysine, biopan P-1487, Jote methylparatolylsulfone,polyvinylpyrrolidone parachloroisocyanel, hydrogen peroxide, stabilizedchlorine dioxide, peracetic acid, copper naphthenate, novalon AG 300,silver chloride, titanium oxide, silver, zinc-calcium phosphate, SilverAce, silver-zinc aluminosilicate, silver-zinc zeolite, novalon AGZ330,phorone killer, dimmer 136, benzalkonium chloride, didecyl dimethylammonium chloride, bardack 2250/80, benzotonium chloride, Hyamine 3500J,cetylammonium bromide, Cetrimide, CTAB, Cetavlon, Dimmer-38,benzalkonium chloride, Hyamine 3500J, BARDAC™ 170P, DC-5700, cetylpyridinium chloride, chitosan, deuron, DCMU, prepentol A6, CMI, 2Cl-OIT,BCM, ZPT, BNP, OIT, IPBC, TCMSP, and the like.

Synthetic pyrethroid insecticides can be preferably exemplified becausean insecticidal effect can be synergically exerted when mixed with theclathrate compound of the present invention. Specific examples of thesynthetic pyrethroid insecticide include acrinathrin, allethrin,bioallethrin, barthrin, bifenthrin, bioethanomethrin, cyclethrin,cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin,deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin,fenpirithrin, fenpropathrin, fenvalerate, esfenvalerate, fluvalinate,tau-fluvalinate, furethrin, imiprothrin, metofluthrin, permethrin,biopermethrin, transpermethrin, phenothrin, prallethrin, profluthrin,pyresmethrin, resmethrin, bioresmethrin, cismethrin, tefluthrin,terallethrin, tetramethrin, tralomethrin, transfluthrin, etofenprox(2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether), flufenprox,halfenprox, protrifenbute, silafluofen, and the like.

2) Concentration Control Method

The concentration control method of the present invention ischaracterized by containing a step of maintaining the saturatedsolubility of the agricultural chemical active ingredient in waterwithin a predetermined concentration range by including the agriculturalchemical active ingredient having ready water-solubility in an interiorspace formed of a polymolecular host compound.

The polymolecular host compound is appropriately selected and theagricultural chemical active ingredient is included in an interior spaceformed of the polymolecular host compound, thereby maintaining thesaturated solubility of the agricultural chemical active ingredient inwater within a predetermined concentration range. When a clathratecompound including an agricultural chemical active ingredient is allowedto exist in water, the concentration of the agricultural chemical activeingredient in water does not reach the saturated concentration of theingredient and can be controlled to a predetermined value that is lowerthan the saturated concentration. The predetermined value is decided byvarious factors, but is preferably controlled by the kind of hostcompound to be used.

The polymolecular host compound and agricultural chemical activeingredient having ready water-solubility to be used are not specificallylimited and examples thereof are the same as those described for theclathrate compound.

3) Agricultural Chemical Formulation

The agricultural chemical formulation of the present inventionpreferably contains the clathrate compound of the present invention.

The agricultural chemical formulation of the present invention ispreferably a seed treatment agent.

The form of the agricultural chemical formulation of the presentinvention is not specifically limited and examples thereof includewettable powders, wettable granules, water-soluble chemicals, granularwater-soluble chemicals, water-soluble liquid formulations, granules,powders, emulsifiable concentrates, water-soluble chemicals, emulsions,suspoemulsions, microcapsules, and sol formulations (also referred to asSC (Suspension Concentrate) agents or flowables). Among these, solformulations are preferable because the clathrate compound of thepresent invention can be maintained in a stable state.

The sol formulation is a formulation obtained by dispersing in water asolid agricultural chemical active ingredient that is insoluble inwater. In the present invention, the agricultural sol formulation can beobtained by dispersing in water the clathrate compound of the presentinvention with a surfactant, a thickener, and, if necessary, otherauxiliaries such as an antifreezing agent.

The content ratio of the clathrate compound is usually from 10 to 60% byweight, and preferably from 25 to 45% by weight, based on the totalweight of the agricultural chemical formulation.

The surfactant is an agent for dispersing the agricultural chemicalactive ingredient, uniformly and stably, for a long period.

The surfactant to be used is not specifically limited, and is preferablya nonionic surfactant or an anionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethersuch as polyoxyethylene lauryl ether, polyoxyethylene alkyl phenylether, polyoxyethylene styryl phenyl ether, polyoxyethylene oleyl ether,polyoxyethylene octyl phenyl ether, sorbitan alkyl ester,polyoxyethylene sorbitan alkyl ester, and mixtures of at least two kindsthereof.

The HLB (hydrophilic-lipophilic balance) value of the nonionicsurfactant is preferably 10 or less, and more preferably 7 or less.

The content ratio of the nonionic surfactant is preferably from 0.1 to20% by weight, and more preferably from 0.1 to 10% by weight, based onthe total weight of the agricultural chemical formulation.

Examples of the anionic surfactant include alkyl sulfate (Na salt, NH₄salt, alkanolamine salt), dialkyl sulfosuccinate (Na salt, Ca salt, Mgsalt), alkyl naphthalenesulfonate, alkylbenzenesulfonate,lignosulfonate, formaldehyde condensate of alkyl naphthalene sulfonate,polyoxyethylene alkyl ether phosphate (Na salt, alkanolamine salt),polycarboxylate, and mixtures of at least two kinds thereof.

The content ratio of the anionic surfactant is preferably from 0.1 to20% by weight, and more preferably from 0.1 to 10% by weight, based onthe total weight of the agricultural chemical formulation.

The thickener is an agent for preventing sedimentation of dispersedparticles.

Examples of the thickener include organic water-soluble polymers such asxanthan gum, guar gum, carboxymethyl cellulose, polyvinyl pyrrolidone,carboxyvinyl polymer, acrylic polymer, starch derivative, andpolysaccharides; and fine powdered solid carriers such as high-puritybentonite and white carbon.

The content ratio of the thickener is preferably from 0.01 to 10% byweight, and more preferably from 0.1 to 3% by weight, based on the totalweight of the agricultural chemical formulation.

Examples of the other auxiliaries include antifreezing agents,antifoamers, and antiseptics. The content ratio of the other auxiliariesis usually from 0 to 15% by weight, and preferably from 0.1 to 8% byweight, based on the total weight of the agricultural chemicalformulation. The addition of the other auxiliaries does not adverselyaffect the saturated solubility of the agricultural chemical activeingredient in water.

The method for preparing a sol formulation is not specifically limitedand examples thereof include a method of dispersing the clathratecompound, a surfactant, a thickener and, if necessary, other auxiliariesin water using a high-speed mixer, and finely pulverizing the obtainedslurry through mechanical pulverizing.

The pulverizing method is not specifically limited, and is preferably awet pulverizing method using a colloid mill, a dyno mill, a ball mill ora sand grinder.

The average particle size of particles in the obtained sol formulationis usually from 0.7 to 2.5 μm, and is preferably from 1 to 2 μm becauseof high stability of the sol.

The sol formulation is likely to form large particles as a result of thegrowth of particles due to a change in temperature during storage(particle growth), or to form a mass as a result of aggregation ofparticles (caking). The sol formulation of the present invention hashigh dispersion stability because the clathrate compound of the presentinvention is used. Since saturated solubility of the agriculturalchemical active ingredient having ready water-solubility is maintainedat a low level, neither particle growth nor caking may occur even whenstored for a long period.

The agricultural chemical formulation of the present invention exhibitsan excellent residual ratio of the agricultural chemical activeingredient in the agricultural chemical formulation even when stored fora long period, because the agricultural chemical active ingredient iscontained as the clathrate compound in the formulation.

According to the agricultural chemical formulation of the presentinvention, the saturated solubility of the agricultural chemical activeingredient having ready water-solubility can be set within apredetermined concentration range by appropriately selecting thepolymolecular host compound to be used.

According to the agricultural chemical formulation of the presentinvention, since the saturated solubility in water of the agriculturalchemical active ingredient having ready water-solubility can bemaintained and controlled at a low level, it is made possible to preventthe agricultural chemical active ingredient from dissolving in waterwithin a short period, and thus dissociating from the formulation. Thatis, elution of the agricultural chemical active ingredient into watercan be controlled and active efficacy as an agricultural chemical can beexhibited for a long period.

The agricultural chemical formulation of the present invention can beused in the same manner as in the case of an application method of aconventionally known agricultural chemical formulation. For example,there can be exemplified a method of immersing seeds of field crops in asolution prepared by diluting a predetermined amount of the agriculturalchemical formulation of the present invention in water for apredetermined time, followed by seeding, more specifically, a method offinely pulverizing the agricultural chemical formulation of the presentinvention to 100 μm or less, dispersing or dissolving the pulverizedagricultural chemical formulation in a solvent, immersing seeds in theobtained solution, and coating the surface of seeds with theagricultural chemical formulation, or a method of seeding seed of fieldcrops, and uniformly spraying a predetermined amount of a solutionprepared by diluting the agricultural chemical formulation of thepresent invention with water.

The agricultural chemical formulation of the present invention containsthe clathrate compound of the present invention and is therefore stablein the soil and also exhibits excellent residual effects.

The agricultural chemical formulation of the present invention can beused for various purposes other than agricultural purposes, for example,soil pest control agents, termite control agents, agents for clothes,pest insect control agents, wood pest insect control agents, baitagents, animal ectoparasite control agents, sanitary pest insect controlagents, domestic communicable disease control agents, ship bottompaints, antialgal agents for fishing nets, antifungal agents for wood,biocides, and the like.

4) Agricultural Active Composition

The agricultural active composition of the present invention containsthe clathrate compound of the present invention and the syntheticpyrethroid insecticide. The synthetic pyrethroid insecticide can exhibita synergistically enhanced insecticidal effect when mixed with theclathrate compound of the present invention.

The content ratio of the synthetic pyrethroid is not specificallylimited, but is usually from 0.05 to 20 parts by weight, preferably from0.1 to 10 parts by weight, and more preferably from 0.2 to 5 parts byweight, based on 1 part by weight of the agricultural chemical activeingredient having ready water-solubility in the clathrate compound ofthe present invention.

The method of mixing the clathrate compound of the present inventionwith the synthetic pyrethroid is not specifically limited, and a methodof mixing the clathrate compound of the present invention with thesynthetic pyrethroid to prepare a formulation, a method of mixing anagricultural chemical formulation containing the clathrate compound ofthe present invention with the synthetic pyrethroid to prepare aformulation, a method of mixing the clathrate compound of the presentinvention with the synthetic pyrethroid and using the obtained mixture(tank-mix), and a method of (successively) treating almostsimultaneously with the application time can all be employed.

EXAMPLES

The present invention will now be described in more detail by examples.However, the present invention is not limited to the following examples.

The melting point was measured using a melting point measuring apparatus(DSC220, manufactured by Seiko Instruments Inc.).

Example 1

24.4 g (110 mmol) of acetamiprid (melting point: 96.4° C.) and 19.9 g(50 mmol) of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP) weredissolved in 500 ml of ethyl acetate while stirring under refluxconditions. After the completion of dissolution, the solution wasstirred for 30 minutes and allowed to stand at room temperatureovernight. The precipitated crystals were collected by filtration toobtain Clathrate compound 1.

The inclusion ratio of the Clathrate compound 1 was as follows:TEP:acetamiprid=1:2, and the melting point was 162.7° C.

¹H-NMR spectrum (CDCl₃, internal standard: TMS) of the Clathratecompound 1 is shown in FIG. 1. In FIG. 1, the ordinate indicates thepeak intensity and the abscissa indicates the chemical shift (ppm) value(the same as in FIG. 4, FIG. 7 and FIG. 10).

The measurement results of XRD of the Clathrate compound 1 are shown inFIG. 2. The ordinate indicates the intensity and the abscissa indicatesthe diffraction angle (the same as in FIG. 5, FIG. 8 and FIG. 12).

The measurement results of TG-DTA of the Clathrate compound 1 are shownin FIG. 3. In FIG. 3, the ordinate (left) indicates the change in weight(% by weight), the ordinate (right) indicates Heat Flow/μV, and theabscissa indicates the temperature (° C.) (the same as in FIG. 6, FIG. 9and FIG. 13).

Example 2

33.0 g (150 mmol) of acetamiprid (melting point: 96.4° C.) and 39.8 g(100 mmol) of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP) weredissolved in 220 ml of methanol while heating under reflux conditions.After the completion of dissolution, the solution was stirred for 30minutes and allowed to stand at room temperature overnight. Theprecipitated crystals were collected by filtration to obtain Clathratecompound 2.

The inclusion ratio of the Clathrate compound 2 was as follows:TEP:acetamiprid:methanol=1:1:1, and the melting point was 167.5° C.

¹H-NMR spectrum (CDCl₃, internal standard: TMS) of the Clathratecompound 2 is shown in FIG. 4, the measurement results of XRD are shownin FIG. 5, and the measurement results of TG-DTA are shown in FIG. 6.

Example 3

33.0 g (150 mmol) of acetamiprid (melting point: 96.4° C.) and 39.8 g(100 mmol) of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP) weredissolved in 220 ml of ethanol while heating under reflux conditions.After the completion of dissolution, the solution was stirred for 30minutes and allowed to stand at room temperature overnight. Theprecipitated crystals were collected by filtration to obtain Clathratecompound 3.

The inclusion ratio of the Clathrate compound 3 was as follows:TEP:acetamiprid:ethanol=1:1:1, and the melting point was 167.5° C.

¹H-NMR spectrum (CDCl₃, internal standard: TMS) of the Clathratecompound 3 is shown in FIG. 7, the measurement results of XRD are shownin FIG. 8, and the measurement results of TG-DTA are shown in FIG. 9.

Example 4

870 mg of acetamiprid (melting point: 96.4° C.), 1.26 g of2,2′,4,4′-tetrahydroxybenzophenone (THB) and 5.7 ml of ethanol weremixed and dissolved while stirring and heating under reflux conditionsfor 30 minutes. The solution was allowed to stand for 168 hours and theprecipitated crystals were collected by filtration to obtain Clathratecompound 4.

¹H-NMR spectrum (CDCl₃, internal standard: TMS) of the Clathratecompound 4 is shown in FIG. 10, IR spectrum (KBr) is shown in FIG. 11,the measurement results of XRD are shown in FIG. 12, and the measurementresults of TG-DTA are shown in FIG. 13. In FIG. 11, the ordinateindicates percentage transmittance and the abscissa indicates a wavenumber (cm⁻¹).

(Measurement of Saturated Solubility)

After weighing a fixed amount of each of the Clathrate compounds 1 to 4obtained in Examples 1 to 4 and an acetamiprid as a control in ameasuring flask, distilled water at 25° C. was added to obtain an equalvolume. After stoppering and up-and-down shaking for 5 times, themeasuring flask was allowed to stand in an incubator at 25° C. Afterup-and-down shaking for 5 times followed by sampling with the passage oftime, water at 25° C. was added to obtain an equal volume again, andsampling was carried out up to 192 hours. The concentration ofacetamiprid in the sampled solution was measured by HPLC and then thesaturated solubility was calculated. The results are shown in Table 1.

As shown in Table 1, the saturated solubility after standing at 25° C.for 192 hours was as follows: Clathrate compound 1; 232 ppm, Clathratecompound 2; 238 ppm, Clathrate compound 3; 230 ppm, Clathrate compound4; 373 ppm, acetamiprid; 3807 ppm.

TABLE 1 Concentration of acetamiprid (ppm) 1 3 24 48 72 192 Compoundshour hours hours hours hours hours Clathrate 121 ppm 134 ppm 193 ppm 210ppm 221 ppm 232 ppm compound 1 Clathrate  72 ppm  79 ppm 161 ppm 200 ppm217 ppm 238 ppm compound 2 Clathrate 156 ppm 156 ppm 163 ppm 179 ppm 200ppm 230 ppm compound 3 Clathrate 238 ppm 244 ppm 306 ppm 333 ppm 346 ppm373 ppm compound 4 Acetamiprid 2,822 ppm   3,273 ppm   3,734 ppm   3,776ppm   3,752 ppm   3,807 ppm  

As is apparent from the results shown in Table 1, the saturatedsolubility of acetamiprid was drastically lowered in the Clathratecompounds 1 to 4. It was also found that the saturated solubility aftera lapse of long period of time (after 192 hours) varied depending on thepolymolecular host compound used and the saturated solubility showedsubstantially the same value (Clathrate compounds 1, 2 and 3) when usingthe same polymolecular host compound, even if the method for preparingthe clathrate compound varied.

Example 5

35.0% by weight of Clathrate compound 1, 5.0% by weight ofpolyoxyethylene lauryl ether (Newcol 2303, manufactured by NipponNyukazai Co., Ltd.) as a surfactant, 2.5% by weight of Na dioctylsulfosuccinate (Newkalgen EP-70G, manufactured by Takemoto Oil & FatCo., Ltd.), 0.2% by weight of a thickener (Roadpole 23, manufactured byRhodia Nicca, Ltd.) and other auxiliaries, that is, 5.0% by weight of anantifreezing agent (propylene glycol), 0.5% by weight of an antifoamer(Antifoam SE39, manufactured by Wacker Asahikasei Silicone Co., Ltd.)and 0.1% by weight of an antiseptic (PROXEL GXL, manufactured by AveciaKK) were mixed with 51.7% by weight of water using a high-speed mixer.The obtained slurry was pulverized using a bead mill to obtain Solformulation 1.

Sol formulation 1 had an average particle size of 1.3 μm.

Example 6

98% by weight of Clathrate compound 1, and 1% by weight of Nalignosulfonate (Newkalgen RX-B, manufactured by Takemoto Oil & Fat Co.,Ltd.) and 1% by weight of Na alkyl naphthalenesulfonate (Newkalgen BX-C,manufactured by Takemoto Oil & Fat Co., Ltd.) as a surfactant were mixedand pulverized using a pin mill to obtain Wettable powder 1 to becontained in a formulation in an amount of 50% by weight.

Storage Stability Test

1 to 2 g of Sol formulation 1 was placed in an ampoule and stored in anincubator at 54° C. for 7 days (a), or alternately stored in incubatorsat 50° C. and −10° C. each for 3 days at 50° C., 3 days at −10° C.,alternating for a total of 30 days (b). The content of acetamiprid wasmeasured by high-performance liquid chromatography (HPLC) and theresidual ratio of acetamiprid in the sol formulations was calculated. Asa result, the residual ratio of acetamiprid in (a) and (b) wassubstantially 100%. This shows that the stability of acetamipridcontained therein can be maintained even if Sol formulation 1 is exposedto an environment where the temperature drastically changes for a longperiod. Sol formulation 1 in (a) had an average particle size of 1.6 μmand showed a lesser particle growth rate, and also caking did not occur.

Also 1 to 2 g of Wettable powder 1 was placed in a vinyl bag and thevinyl bag was placed in an aluminum laminate, and then the storagestability test (a) was carried out. As a result, the residual ratio ofacetamiprid was substantially 100%, similarly to Sol formulation 1.After the test, the state of the powder was excellent and caking alsodid not occur.

Stability in Soil Test

The obtained wettable powder 1 was uniformly mixed with soil so as tocontrol the content of acetamiprid to 1 mg based on 10 g of the soil.After storing in an incubator under the conditions of a temperature of25° C. and a relative humidity of 90%, sampling was carried out everypredetermined period. Acetamiprid in the soil was extracted with asolvent and analyzed by HPLC, and thus the residual ratio of acetamipridwas calculated.

The same test was carried out using a wettable powder containing 70% byweight of acetamiprid and the stability in soil (residual ratio) wasmeasured. The results are shown in Table 2. In Table 2, half-life in thesoil means the period (days) required to reduce the amount ofacetamiprid added under these test conditions to half.

TABLE 2 Wettable powder containing Lapsed days Wettable powder 1 70% byweight of acetamiprid  0 day 100%  100%   7 days 46% 47% 13 days 45% 35%21 days 27% 23% 28 days 28% 20% Half-life in 12.6 days 10.5 days soil

As is apparent from the results in Table 2, the half-life in soil ofacetamiprid in Wettable powder 1 was longer than that of acetamiprid inthe wettable powder containing 70% by weight of acetamiprid, andWettable powder 1 had high stability in soil.

Test as Seed Treatment Agent

In to 3 ml of a solution (sticker solution) prepared by dissolving 5% byweight of polyvinyl alcohol (Gohsenol GL-05S, manufactured by NipponSynthetic Chemical Industry Co., Ltd.) and 1% by weight of Nalignosulfonate (Newkalgen RX-B, manufactured by Takemoto Oil & Fat Co.,Ltd.) as a surfactant in 94% by weight of water, Wettable powder 1 ofExample 6 was dispersed so as to contain 70 mg of acetamiprid, and then0.3 ml of this dispersion was placed in a vinyl bag with a zippercontaining 20 g of wheat seeds (Norin No. 61). Immediately after that,the vinyl bag was closed, and the seeds were coated with the chemical byvigorously shaking for 30 seconds. These seeds were spread over a trayand then air-dried at room temperature overnight to obtain wheat seedscoated with 35 g of acetamiprid per 100 kg of seeds. The seeds were thenplanted in a No. 2 unglazed flower pot containing Kuroboku soil,followed by inoculation with adults and larvae of 20 wheat aphids perplant 40 days (or 50 days) later. The number of parasites was counted 2,4, and 7 days after inoculation to evaluate the residual efficacy. Inthe case of treatment with a wettable powder containing 70% by weight ofacetamiprid and no treatment as control, the same test was carried out.The results are shown in Table 3.

TABLE 3 Inoculated 40 days Inoculated 50 days after seeding afterseeding after after after after after after Formulations 2 days 4 days 7days 2 days 4 days 7 days Wettable 2 0 0 19 29 32 powder 1 Wettable 7 738 40 43 76 powder containing 70% by weight of acetamiprid No treatment49 87 276 43 90 159

As is apparent from the results shown in Table 3, Wettable powder 1exhibited high persistence of potency of an agricultural chemical activeingredient, compared with the wettable powder containing 70% by weightof acetamiprid.

Test as a Seed Treatment Agent Used in Combination with a SyntheticPyrethroid Agent

In 3.2 ml of a solution (sticker solution) prepared by dissolving 5% byweight of polyvinyl alcohol (Gohsenol GL-05S, manufactured by NipponSynthetic Chemical Industry Co., Ltd.) and 1% by weight of Nalignosulfonate (Newkalgen RX-B, manufactured by Takemoto Oil & Fat Co.,Ltd.) as a surfactant in 94% by weight of water, Wettable powder 1 ofExample 6 was dispersed so as to contain 800 mg of acetamiprid, and then0.24 g of this dispersion was placed in a vinyl bag with a zippercontaining 8 g of rapeseeds. Immediately after that, the vinyl bag wasclosed, and the rapeseeds were coated with the chemical by vigorouslyshaking for 30 seconds. These seeds were spread over a tray and thenair-dried at room temperature overnight to obtain rapeseeds coated with500 g of acetamiprid per 100 kg of seeds.

In 1.1 g of bifenthrin SC agent (active ingredient: 7.2% by weight),Wettable powder 1 of Example 6 was dispersed so as to contain 80 mg ofacetamiprid, and then 0.64 g of this dispersion (containing 40 mg ofbifenthrin and 40 mg of acetamiprid) was placed in a vinyl bag with azipper containing 8 g of rapeseeds. Immediately after that, the vinylbag was closed, and the rapeseeds were coated with the chemical byvigorously shaking for 30 seconds. These seeds were spread over a trayand then air-dried at room temperature overnight to obtain rapeseedscoated with 500 g of bifenthrin and 500 g of acetamiprid per 100 kg ofseeds.

The obtained seeds were seeded in a No. 2 pot containing alluvial soiland then cultivated in a greenhouse. 15 days after seeding, rapeseedlings were transferred to a cage in which 100 imagines of stripedflea beetle were released. 2 days after standing, the number ofincidences of insect damage due to imagines of striped flea beetle of 3plants in each experimental plot was counted. In the case of a treatmentwith a wettable powder containing 70% by weight of acetamiprid or only abifenthrin SC agent so as to coat seeds with 500 g of the activeingredient thereof per 100 kg of seeds, and no treatment as control, thesame test was carried out. The results are shown in Table 4.

TABLE 4 Number of incidences of insect damage/ Insecticidal 3 plantsratio % Treatment amount after 15 after 15 Formulations g/100 kg ofseeds days days Wettable powder 1 + 500 + 500 40 89.9 bifenthrin 250 +250 58 85.4 Wettable powder 1 500 65 83.7 Bifenthrin 500 98 75.4Wettable powder 500 80 79.9 containing 70% by weight of acetamiprid Notreatment — 398

As is apparent from the results shown in Table 4, Wettable powder 1exhibited a higher insecticidal effect against striped flea beetlescompared with the wettable powder containing 70% by weight ofacetamiprid. It was also found that the insecticidal effect againststriped flea beetles was enhanced by using in combination withbifenthrin as a synthetic pyrethroid agent, compared with a treatmentwith only Wettable powder 1 or bifenthrin, and that a synergistic effectwas recognized between Wettable powder 1 and the synthetic pyrethroidagent.

Test as an Agent Against Termites

[Potency Test as a Soil Treatment Agent Against Termites]

A chemical solution was prepared by dispersing 0.5 g of Wettable powder1 obtained in Example 6 in 1.6 L of tap water. 1 ml of the obtainedchemical solution was added to 14 g of kuroboku soil, followed byuniform mixing with stirring. The treated soil was placed in anincubator at 36° C. and water lost by evaporation was added every 7days, so as to return to the initial weight, followed by mixing whilestirring. 21 days after the treatment, the treated soil was filled in avinyl chloride tube (inner diameter: 11 mm, length: 5 cm) and the tubewas connected to the bridge portion in height of 2 cm from the bottom oftwo PET resin test vessels (inner diameter: 5 cm, height: 11 cm). In onetest vessel, 30 g of a non-treated soil was placed. After 2 days, 60worker ants and one soldier ant of the Reticulitermes speratus Kolbespecies were inoculated. In the other test vessel, 5 g of cut corrugatedcardboard as bait and 5 ml of tap water were placed. The test vessel wasplaced in an incubator at 25° C. and the active efficacy was evaluatedby observing the state of boring of the treated soil, the state ofbehavior and the state of health for 21 days. A plot treated with awettable powder containing 70% by weight of acetamiprid (the same amountof active ingredient) and a plot treated with no chemical were used ascontrol. The test was repeated twice. The results are shown in Table 5.

TABLE 5 Boring degree* Repe- 1 3 5 7 10 14 21 Formulations tition DATDAT DAT DAT DAT DAT DAT Wettable A 1 1 1 1 1 1 1 powder B 0 0 0 0 0 0 0Average 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Wettable A 0 0 5 5 5 5 5 powder B 11 2 2 3 5 5 containing Average 0.5 0.5 3.5 3.5 4 5 5 70% by weight ofacetamiprid No treatment A 5 5 5 5 5 5 5 B 5 5 5 5 5 5 5 Average 5 5 5 55 5 5 *Boring degree 0: no boring to test soil was observed Boringdegree 1: boring distance of less than 1 cm Boring degree 2: boringdistance of less than 2 cm Boring degree 3: boring distance of less than3 cm Boring degree 4: boring distance of less than 4 cm Boring degree 5:boring distance of not less than 4 cm

As is apparent from the results shown in Table 5, Wettable powder 1exhibited enhanced insecticidal effects on the soil againstReticulitermes speratus Kolbe compared with the wettable powdercontaining 70% by weight of acetamiprid.

1. A clathrate compound, comprising: a polymolecular host compound as ahost compound; and an agricultural chemical active ingredient having asaturated solubility in water at 25° C. of not less than 500 ppm as aguest compound; wherein the polymolecular host compound is atetrakisphenol compound represented by formula (I):

where: X represents: (CH₂)_(n) where n represents an integer of 0 to 3,or a phenylene group which may have a substituent; and R¹ to R⁸ eachindependently represents: a hydrogen atom, an alkyl group having 1 to 6carbon atoms, a phenyl group which may have a substituent, a halogenatom, or an alkoxyl group having 1 to 6 carbon atoms.
 2. A clathratecompound, comprising: a polymolecular host compound as a host compound;and an agricultural chemical active ingredient having a saturatedsolubility in water at 25° C. of not less than 500 ppm as a guestcompound; wherein the polymolecular host compound is ahydroxybenzophenone compound represented by formula (II):

where: R⁹ and R¹⁹ each independently represents: an alkyl group having 1to 6 carbon atoms, a halogen atom, or an alkoxyl group having 1 to 6carbon atoms; r and s each independently represents an integer of 0 to4; and p and q each independently represents an integer of 1 to
 4. 3.The clathrate compound according to claim 1, wherein the agriculturalchemical active ingredient is a neonicotinoid compound.
 4. The clathratecompound according to claim 3, wherein the neonicotinoid compound is atleast one selected from the group consisting of nitenpyram,imidacloprid, acetamiprid, thiamethoxam, clotianidin, thiacloprid, anddinotefuran.
 5. The clathrate compound according to claim 2, wherein theagricultural chemical active ingredient is a neonicotinoid compound. 6.The clathrate compound according to claim 5, wherein the neonicotinoidcompound is at least one selected from the group consisting ofnitenpyram, imidacloprid, acetamiprid, thiamethoxam, clotianidin,thiacloprid, and dinotefuran.